CN104487612A - Thermal barrier coating system with porous tungsten bronze structured underlayer - Google Patents

Thermal barrier coating system with porous tungsten bronze structured underlayer Download PDF

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Publication number
CN104487612A
CN104487612A CN201380009125.4A CN201380009125A CN104487612A CN 104487612 A CN104487612 A CN 104487612A CN 201380009125 A CN201380009125 A CN 201380009125A CN 104487612 A CN104487612 A CN 104487612A
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thermal barrier
layer
65mol
25mol
coating
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CN104487612B (en
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大卫·B·艾伦
阿南德·A·库尔卡尼
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Siemens AG
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Siemens AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/044—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material coatings specially adapted for cutting tools or wear applications
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • C01P2006/14—Pore volume
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D11/00—Preventing or minimising internal leakage of working-fluid, e.g. between stages
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D11/00—Preventing or minimising internal leakage of working-fluid, e.g. between stages
    • F01D11/08—Preventing or minimising internal leakage of working-fluid, e.g. between stages for sealing space between rotor blade tips and stator
    • F01D11/12—Preventing or minimising internal leakage of working-fluid, e.g. between stages for sealing space between rotor blade tips and stator using a rubstrip, e.g. erodible. deformable or resiliently-biased part
    • F01D11/122—Preventing or minimising internal leakage of working-fluid, e.g. between stages for sealing space between rotor blade tips and stator using a rubstrip, e.g. erodible. deformable or resiliently-biased part with erodable or abradable material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
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  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

A system of layers in a protective coating (20) for a substrate (22), including at least an outer thermal barrier layer (32) and a tungsten bronze structure ceramic underlayer (30) that reduces spalling of the outer layer. The range of materials for the underlayer includes ceramics of the form Ba6-3m Re8+2m Ti18 O54, where 0<m<1.5, and Re is any rare earth element or mixture thereof. These underlayer materials reduce spalling of the thermal barrier layer, and thus extend the life of the coating system. In some embodiments, materials for the outer thermal barrier layer may include Yttria-stabilized Zirconia (YSZ) or ceramics with lower thermal conductivity than YSZ. A segmented YSZ layer (26) is provided in some embodiments for additional thermal expansion compliance.

Description

There is the thermal barrier coating system of POROUS TUNGSTEN bronze structures bottom
Technical field
The present invention relates to thermal barrier coating, particularly relate to for gas turbine engine component peel off minimizing wear away (abradable) thermal barrier coating.
Background technology
The turbine section of gas turbine engine comprises as the fixing part of outer shroud and the sealing face for reducing the inter-stage gas leakage through turbine tip.In industrial gas turbines (IGT), these fixing parts are called " ring section ", and it is called as " blade exterior air seals " or BOAS in aircraft engine.Thermal technology does aviation in gas path and IGT parts both scribble anti-oxidant metal layer and one deck or more the layer thermal isolation ceramic coating being called and engaging coating.In addition, outermost ceramic layer has a mind to carry out spraying using can as the clearance control coating (clearance control coating) being known as abradable coating with low density (porous).When metallic turbine blade and porous abradable coating occur to rub, blade by when not damaged blade through coating, thus make the gap between blade tip and ring section tightr to make the leakage of hot gasses between stage of turbine minimize.This both has beneficial effect to power stage and fuel efficiency, and therefore abradable coating is extremely important for engine design.
It is many that abradable coating sprays thick than the thermal barrier coating of other types usually, and reason is that the thickness of abradable coating needs to make blade tip with in the amount expected incision coating.Along with the increase of coat-thickness, to start and the period thermal strain in the coating that kills engine also increases.This can cause peeling off of abradable coating, and clearance control (engine power and efficiency) and Thermal protection (metal ring section work-ing life) both losses.
Accompanying drawing explanation
Based on accompanying drawing, the present invention will be described in the following description, and described accompanying drawing illustrates:
Fig. 1 shows the coat system layering of the exemplary 1,5 and 9 in explanatory view 5.
Fig. 2 shows the coat system layering of the exemplary 2 and 6 in explanatory view 5.
Fig. 3 shows the coat system layering of the exemplary 3 and 7 in explanatory view 5.
Fig. 4 shows the coat system layering of the exemplary 4 and 8 in explanatory view 5.
Fig. 5 illustrates the list of exemplary of the present invention.
Fig. 6 illustrates the comparative test result between prior art coating and coat system of the present invention.
Detailed description of the invention
The invention provides a kind of layer system for hot gas path turbine components, comprise the bottom for thermal barrier coatings can be worn away of the coating performance providing improvement compared with the abradable coating of prior art.In this article in order to element clear for the purpose of, term " thermal barrier coating " (TBC) refers to the whole coating comprising all layers; And " thermal barrier coatings " (TBL) refers to the outermost layer of coating; " barrier material " (TBM) refers to the material of TBL.
In open US 2009/0258247 A1 of patent application, the present inventor describes a series of outermost that is of value to can the tungsten bronze structured ceramic material of wearing course, reason to be these materials be can wear away and there is phase stability and anti-agglutinatting property up to when 1400 DEG C, thus resist densification when gas turbine service temperature.The present inventor has now found that these materials can be advantageously used for the bottom below the worn away TBL of tradition or advanced person, traditional worn away TBL is the zirconium white (being YSZ in this article) of the stabilized with yttrium oxide of 7mol.% to 9mol.%, and the worn away TBL of advanced person is the zirconic acid ytterbium (being YBZO in this article) of the hafnium acid gadolinium (being GHO in this article) of pyrrhite system such as 25mol% to 65mol%, the gadolinium zirconate (being GZO in this article) of 25mol% to 65mol% and/or 25mol% to 65mol%.Scope for the material of bottom comprises Ba 6-3mre 8+2mti 18o 54the pottery of form, wherein 0<m<1.5, and Re is any rare earth element or its mixture.These materials comprise the BaNd that compound such as tool is with or without the rare earth dopant that its thermal conductivity is reduced 2ti 4o 12(being BNT in this article), and Ba (Nd 1.2sm 0.4gd 0.4) Ti 4o 12.Usually these materials are referred to herein as " B3 ", and are commonly referred to be tungsten bronze structure ceramic.These primers not by means of only providing mechanical compliance to decrease peeling off of TBL, and its also present itself intrinsic abradability make its when penetrated by blade tip or due to above cover TBL wearing and tearing and expose time be used as can wear material.Thus, when compared with prior art coating, the TBL of whole thickness and bottom provide the abradability of enhancing.
Various layer of the present invention applies by thermospray or other known technology.Vesicular structure in layer can produce by easily burning the introducing thing of mistake (fugitive) and/or hollow ceramic ball or other modes.The outermost porous that B3 layer can be applied to as the clearance control coating in gas turbine ring section can wear away below TBL.As a kind of mode in life-span of coat system increasing layer as a whole, the bottom characteristic of B3 give outer can wear away that TBL provides the excellence that can work independent of the abradability of B3 itself peel off the life-span.B3 layer can have at least 5% in various embodiments, or 5% to 35%, or the porosity of 25% to 35% is heat insulation and compatible with the thermal expansion of adjacent porous layer to increase.
Fig. 1 to Fig. 5 illustrates and lists exemplary of the present invention.In order to the additional thermal expansion compatibility (compliance) between substrate 22 and upper strata 28 to 32, provide segmented layer 26 in some embodiments." segmented layer " herein refers to as lower floor: this layer is that the groove of at least 50% of segmented layer or crack are divided into multiple sections by the degree of depth, thus defines the section that overall dimension is not more than 5 times of the degree of depth of segmented layer.
Fig. 1 shows the layering in the thermal barrier coating system 20 of the exemplary 1,5 and 9 in explanatory view 5, and this layering comprises substrate 22; Engage coating 24 such as MCrAlY, wherein M refers to Co, Ni or CoNi; Segmentation YSZ layer 26; Porous ysz layer 28; Porous B3 layer 30; And last porous thermal barrier coatings 32 such as YSZ, YBZO, GZO or GHO.
Fig. 2 shows the layering of the thermal barrier coating 20 of the exemplary 2 and 6 in explanatory view 5, and this layering comprises substrate 22; Engage coating 24 such as MCrAlY; Segmentation YSZ layer 26; Porous B3 layer 30; And last porous thermal barrier coatings 32 such as YSZ, YBZO, GZO or GHO.
Fig. 3 shows the layering of the thermal barrier coating 20 of the exemplary 3 and 7 in explanatory view 5, and this layering comprises substrate 22; Engage coating 24 such as MCrAlY; Porous ysz layer 28; Porous B3 layer 30; And last porous thermal barrier coatings 32 such as YSZ, YBZO, GZO or GHO.
Fig. 4 shows the layering of the thermal barrier coating of the exemplary 4 and 8 in explanatory view 5, and this layering comprises substrate 22; Engage coating 24 such as MCrAlY; Porous B3 layer 30; And last porous thermal barrier coatings 32 such as YSZ, YBZO, GZO or GHO.
Specific embodiment of the invention scheme can in order to the particular benefits in specific design and environment Choice and design.Such as, compared with YBZO TBL, GZO TBL or GHO TBL, 8YSZ TBL has lower abradability.But 8YSZ TBL is cheaply a lot, and the industrial gas turbines thus for old-fashioned, ripe framework can be preferred.Compared with 8YSZ TBL, YBZO TBL is very expensive and have less erosion resistance, so YBZO TBL is most important standard for abradability and the not too important application of cost and resistance to fouling can be preferred selection.
The selection of top abradable coating (TBL) also highly relies on the engine condition of this position.Such as, it may be crucial that the pyrrhite with the advanced person of bottom B3 and segmented layer as shown in Figure 1 can wear away the ring section of TBL to 1 row and 2 rows that expect high-temperature stability and anti-agglutinatting property in the TBL that can wear away at top, and engages at TBC-the resistance of crack propagation that coating interface place provides increase at the ring section punishment section bottom 26 of 1 row and 2 rows.
Another advantage as the more high-layer in Fig. 1 is that it makes interlayer compatibility maximize.This has compared with small―gap suture change and/or is expecting that in the turbine area of large total coat-thickness or design can be preferred.Segmented layer 26 can have the density (not comprising groove or the crackle of segmentation) being greater than 95% in stupalith is own, cause the very high resistance to fracture avoiding occurring crack at TBC-tie layer interface place, thus enhance TBC resistance to flaking.
As the lower number of plies in Fig. 4 makes to have thicker worn away TBL32 and/or thicker bottom B3 in total coat-thickness.This can be preferred in the turbine design having the change of larger gap and/or must limit total coat-thickness.
What Fig. 6 compared a series of thermal cycling test periods test of three kinds of coatings in the scope of gas turbine service temperature peels off the life-span.Peel off data pin to following 3 systems:
Curve 36=engages coating+segmentation 8YSZ+ porous 8YSZ TBL
Curve 38=engages coating+porous 8YSZ+ porous YBZO TBL
Curve 40=engages coating+porous 8YSZ TBL+ porous B3TBL
HVOF CoNiCrAlY is used to engage coating by all three kinds of coating sprayings on Hast-X key (button).Porous BNT B3 coating obtains curve 40 above.Porous BNT B3 coating presents to compare peeling off the life-span and peeling off the life-span the second temperature 44 times long 50% the first temperature 42 times long 100% with YBZO (trace 38) with 8YSZ (trace 36).This increase of peeling off the life-span can make coating life double under certain conditions, thus adds maintenance period and reduce cost.In other words, it can make the service temperature in engine increase by 30 DEG C to 50 DEG C to increase motor efficiency.Therefore, B3 layer described herein is useful as the bottom of other abradable coating systems.
Due to the strongly adherent between B3 material and TBL and due to the mechanical stress in the physical compatibility of thermal cycling period B3 material and coat system 20, B3 bottom 30 provides resistance to flaking for wearing away TBL32.This compatibility decreases otherwise by due to the different thermal expansion between substrate and TBC and due to the wearing and tearing of TBL and particle encounter and the stress be present in TBL30 and TBC20.The densification due to the sintering caused by High Operating Temperature and thermal cycling kept out by B3 material herein.Thus, B3 bottom 30 remains its compatibility in the temperature range larger than 8YSZ, stress reduces and the characteristic of abradability, becomes the better selection for bottom compared with traditional 8YSZ.And, as previously mentioned in this application, compared with the 8YSZ TBL of similar density, tungsten bronze(s) material has higher congenital abradability, if blade penetrates outer YBZOTBL, GZO TBL or GHO TBL layer completely, then 8YSZ TBL has the advantage (with reference to open US 2009/0258247 A1 of patent application) reducing blade wear.In conjunction with the resistance to flaking of the excellence of tungsten bronze(s) (B3) material, be defined as the favourable selection of the bottom for TBL system can be worn away.
Although illustrated in this article and described various embodiments of the present invention, will be apparent that, such embodiment provides by means of only the mode of embodiment.When not departing from invention herein, many modification, change and replacement can be made.Therefore, want, the present invention limits by means of only the spirit and scope of claims.

Claims (20)

1. a thermal barrier coating, comprising:
The bottom of tungsten bronze structured ceramic material; And
Barrier material layer on described bottom.
2. thermal barrier coating according to claim 1, wherein, described bottom comprises Ba 6-3mrE 8+2mti 18o 54, wherein, 0<m<1.5, and RE represents arbitrary rare earth element or its mixture.
3. thermal barrier coating according to claim 1, wherein said bottom comprises BaNd 2ti 4o 12, described BaNd 2ti 4o 12tool is with or without and makes described BaNd 2ti 4o 12thermal conductivity reduce rare earth dopant.
4. thermal barrier coating according to claim 1, wherein said bottom comprises Ba (Nd 1.2sm 0.4gd 0.4) Ti 4o 12.
5. thermal barrier coating according to claim 1, wherein, the porosity of described bottom is 5% to 35%, and comprises Ba 6-3mrE 8+2mti 18o 54, wherein, 0<m<1.5 and RE represents arbitrary rare earth element or its mixture.
6. thermal barrier coating according to claim 5, the porosity of wherein said bottom is 25% to 35%.
7. thermal barrier coating according to claim 5, also comprise the segmented layer in suprabasil joint coating and described joint coating, wherein, described bottom is arranged in described segmented layer.
8. thermal barrier coating according to claim 1, also comprises:
Described bottom to comprise in following group one of at least: 1) primer Ba 6-3mrE 8+2mti 18o 54, wherein, 0<m<1.5, and RE represents any rare earth element or its mixture; And 2) primer BaNd 2ti 4o 12, described primer BaNd 2ti 4o 12have and make described primer BaNd 2ti 4o 12thermal conductivity reduce rare earth dopant, and
Wherein, described barrier material comprises the zirconium white (YSZ) of the stabilized with yttrium oxide of 7mol.% to 9mol.% or has the pottery of the thermal conductivity lower than described YSZ, and the porosity of described bottom is at least 5%.
9. thermal barrier coating according to claim 8, wherein said barrier material comprises the GHO of the YBZO of 25mol% to 65mol%, the GZO of 25mol% to 65mol% or 25mol% to 65mol%.
10. thermal barrier coating according to claim 8, the porosity of wherein said bottom is 25% to 35%, and the porosity of described thermal barrier coatings is 25% to 35%.
11. thermal barrier coatings according to claim 10, also comprise suprabasil joint coating, and the density in described joint coating is greater than the zirconic segmented layer of the stabilized with yttrium oxide of 95%, and wherein said bottom is arranged in described segmented layer.
12. thermal barrier coatings according to claim 8, comprise the layer of following order:
In suprabasil joint coating;
The segmented layer containing YSZ in described joint coating;
The third layer of the porous YSZ in described segmented layer; And
In described third layer and porosity be 5% to 35% described bottom.
13. thermal barrier coatings according to claim 12, wherein said TBM comprises the GHO of the YBZO of 25mol% to 65mol%, the GZO of 25mol% to 65mol% or 25mol% to 65mol%.
14. thermal barrier coatings according to claim 8, comprise the layer of following order;
In suprabasil joint coating;
The segmented layer containing YSZ in described joint coating; And
In described segmented layer and porosity be 5% to 35% described bottom.
15. thermal barrier coatings according to claim 14, wherein said TBM comprises the GHO of the YBZO of 25mol% to 65mol%, the GZO of 25mol% to 65mol% or 25mol% to 65mol%.
16. thermal barrier coatings according to claim 8, comprise the layer of following order;
In suprabasil joint coating;
Porosity in described joint coating is the third layer of the YSZ of 8% to 15%; And
Porosity in described third layer is the described bottom of 25% to 35%.
17. thermal barrier coatings according to claim 16, wherein said TBM comprises YBZO, the 25mol% to 65mol%GZO of 25mol% to 65mol% or the GHO of 25mol% to 65mol%.
18. thermal barrier coatings according to claim 8, comprise the layer of following order:
In suprabasil joint coating;
Porosity in described joint coating is the described bottom of 25% to 35%.
19. thermal barrier coatings according to claim 18, wherein said TBM comprises the GHO of the YBZO of 25mol% to 65mol%, the GZO of 25mol% to 65mol% or 25mol% to 65mol%.
20. 1 kinds of thermal barrier coatings, comprising:
As the barrier material layer of top layer; And
The porosity be arranged in below described top layer is the B3 material layer of at least 5%.
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